Hyperbranched polyesters

ABSTRACT

This invention relates to hyperbranched, functional polyesters.

This is a division of application Ser. No. 07/865,599, filed Apr. 9,1992, now U.S. Pat. No. 5,183,862, which is a division of applicationSer. No. 07/548,681, filed Jun. 22, 1990, now U.S. Pat. No. 5,136,014.

FIELD OF THE INVENTION

This invention relates to hyperbranched, functional polyesters.

BACKGROUND OF THE INVENTION

Baker et al., U.S. Pat. No. 3,669,939 disclose highly branchedcondensation polymers prepared from polyhydroxymonocarboxylic acids(OH)_(n) R--CO₂ H wherein R is a hydrocarbon radical of up to 22 carbonatoms optionally interrupted by a heteroatom, and n is 2-6. Monomersdisclosed as particularly suitable are those of the formula(HOCH₂)_(2--C)(R³)CO₂ H wherein R³ is alkyl or --CH₂ OH. Aromaticmonomers are not exemplified.

P. J. Flory, J. Amer. Chem. Soc., 74, 2718 (1952), "Principles ofPolymer Chemistry", Cornell University Press, 1953, pp. 361-370,discusses the theory of condensation polymerization of so-called AB_(n)-type monomers wherein A and B functions condense together to formbranched high polymers which attain high molecular weight withoutgelation. The theory predicts that polymerization of such monomerscontaining one A and Bn functions leads to randomly branched polymerscontaining one unreacted A function and (n-1)x+1 unreacted B functionswhere x is the number of monomer units, said polymers being morepolydisperse the higher the degree of polymerization. Examples ofmonomers of this type given by Flory are benzyl halides XCH₂ --C₆ H₅,alkali metal salts of trihalophenols and D-glucose; the polymers aresaid to be soluble, non-crystalline and fusible when correctly prepared.Fully aromatic monomers of the AB_(n) -type, or polymers therefrom, arenot disclosed.

Maciejewski, J., Macromol. Sci.-Chem., A17 (4), 689 (1982) describes hisconcept of so-called shell topological compounds, preparation of whichincludes polymerization of a monomer of the XRY_(n) -type, wherein n isat least 2. Such polymerization results in a "cascade branched(uncrosslinked) molecule of spherical structure". Equations are providedwhich correlate, among other properties, molecular weight with spherediameter. Although monomers employed in the present invention are of theXRY_(n) -type, the reference does not suggest polymerization of arylenemonomers Or the physical properties of the polyarylenes therefrom.

Tomalia et al., U.S. Pat. Nos. 4,587,329; 4,568,737; 4,588,120;4,507,466 and WO 84/02705 disclose dense star polymers containing core,core branches and terminal groups. These polymers are built up, layerafter layer, from a core substance by selective condensation offunctional groups; each successive layer becomes a core for thesubsequent layer. Only aliphatic polyamides and polyethers areexemplified. The monomers are of the AB_(n) -type and the polymerstherefrom are said to be Q soluble and to have a molecular volume lessthan 80% of that of a conventional extended star polymer made fromsimilar materials, molecular diameters being less than 2000 angstromunits.

U.K. Patent Application GB 2,132,626 discloses a method for producingaromatic polyesters by polycondensation of A: aromatic hydroxycarboxylicacids, or A with B: one or more compounds selected from aromaticdicarboxylic acids and C: one or more compounds selected from aromaticdiphenols, and on said polycondensation, adding D: one or more compoundsselected from the group consisting of aromatic trihydroxy compounds,aromatic dihydroxy-monocarboxylic acids and aromaticmonohydroxydicarboxylic acids.

Kricheldorf et al., Polymer [11], 23, 1821 (1982) disclose thepreparation of branched poly(3-hydroxybenzoate) by condensation of3-(trimethylsiloxy)benzoyl chloride and 3,5-(bistrimethylsiloxy)benzoylchloride, said polycondensate remaining uncrosslinked regardless ofdegree of conversion.

The prior art does not disclose soluble, highly branched polyestersprepared by self-polycondensation of AB_(n) -type monomers wherein n isat least 2 and wherein B moieties contain a terminal carboxylic acidgroup or derivative thereof, or wherein either A or B is a carboxyl orhydroxyl-terminated moiety which is an aromatic or aliphatic amino. Bysoluble is meant that the polyester is soluble to at least 5% insolvents such as tetrahydrofuran, dimethylacetamide, acetone, chloroformor hexafluoroisopropanol.

SUMMARY OF THE INVENTION

The present invention provides:

(1) the soluble, hyperbranched polyester having at least one branch per10 monomer units prepared in a process comprising polycondensation ofone or more monomers of the formula:

    XR.sup.2 [(R.sup.1).sub.m Y].sub.n (I)

wherein;

R¹ is a divalent C₁₋₁₂ hydrocarbyl radical which is linear or branchedaliphatic, alicyclic, aromatic or mixed aromatic-aliphatic;

R² is a C₁₋₁₂ hydrocarbyl radical having a valence of (n+1), saidradical being linear or branched aliphatic, alicyclic, aromatic or mixedaromatic-aliphatic, or R³ N wherein R³ is defined as for R¹ ;

either of R¹ , R² or R³ optionally also containing substituents that areunreactive under processing conditions, i.e., the polycondensation andrecovery conditions,

X and Y are terminal functions selected from --CO₂ R' and --OR" whereinR' is H Or C₁₋₁₂ alkyl and R" is H Or OC(O)R;

m is 0 or 1; and

n is an integer and is at least 2;

with the provisos that:

(i) both X and Y are not --CO₂ R' or --OR.increment.;

(ii) no X or Y function is adjacent to another X or Y function;

(iii) when R² is an aliphatic hydrocarbyl radical, Y is --CO₂ R'; and

(iv) when R² is R³ N, m is 1.

This invention also provides:

(2) the soluble hyperbranched polyester prepared from one or moremonomers of Formula I wherein residual terminal functions (X and Ygroups) have been chemically capped;

(3) the hyperbranched polyester of (1) that has been linearly linked orcrosslinked;

(4) copolymers of the hyperbranched polyester of (1) with diols ordicarboxylic acids;

(5) a stable dispersion of the soluble hyperbranched polymer of (1), (2)or (4) above;

(6) process of using the soluble hyperbranched polymer of (1), (2) or(4) in a drug delivery system; and

(7) process of using the soluble hyperbranched polymer of (1), (2) or(4) as a rheology modifier.

Another embodiment of the invention is the capped polyester produced bycapping with a monofunctional capping agent the X and Y functions of ahyperbranched polyester having at least 1 branch per 10 monomer unitsprepared by conventional polycondensation of one or more monomers of theformula:

    XR.sup.2 [(R.sup.1).sub.m Y]n (II)

wherein:

R¹ is a divalent C₁₋₁₂ hydrocarbyl radical which is linear or branchedaliphatic, alicyclic, aromatic or mixed aromatic-aliphatic;

R² is a C₁₋₁₂ hydrocarbyl radical having a valence of (n+1), saidradical being linear or branched aliphatic;

either of R¹ or R² optionally also containing substituents that areunreactive under processing conditions;

X is --CO₂ R';

Y is --OR.increment.;

wherein

R' is H or C₁₋₁₂ alkyl and R.increment. is H or OC(O)R;

m is 0 or 1; and

n is an integer and is at least 2;

with the proviso that:

no X or Y function is adjacent to another X or Y function.

This embodiment also covers the above polyester that has been linearlylinked or crosslinked or copolymers of the polyester with diols ordicarboxylic acids.

DETAILS OF THE INVENTION

Monomers of Formula I wherein R² is R³ N are good yield by refluxing theappropriate α, β unsaturated alkyl ester with the appropriate aminoalcohol in a suitable solvent such as methanol; e.g.,

    HOR.sup.3 NH.sub.2 +CH.sub.2 =CHCOOR'→HOR.sup.3 N(CH.sub.2 CH.sub.2 COOR').sub.2

    NH(R.sup.1 OH).sub.2 +CH.sub.2 =CHCOOR'→(HOR.sup.1).sub.2 NCH.sub.2 CH.sub.2 COOR'.

Monomers of Formulae I or II wherein R² is an aromatic moiety arepreferably employed as the acyl esters (R' is OC(O)R'). Such esters maybe prepared from the corresponding alcohols using conventionaltechniques for acylation, such as, for example, acetic anhydride withsulfuric acid catalyst. Cycloaliphatic monomers of Formulae I or II maybe prepared using conventional organic synthetic methods includingdirect hydrogenation of aromatic rings using an appropriatehydrogenation catalyst. Other monomers of Formulae I and II are known orobvious compounds prepared by conventional methods, e.g., as disclosedin U.S. Pat. No. 3,669,939.

As previously indicated, R¹, R² and R³ can contain substituents, e.g.,halogen, lower alkyl, that are not reactive under the polycondensationand recovery conditions.

The soluble hyperbranched polyesters (HBP-1) of the invention areprepared by the conventional self-condensation polymerization of one ormore monomers of Formulae I or II wherein said monomers are heated at atemperature in the range of 100° C. to 325° C. with vacuum (0.5 mm Hg;133 Pa) being applied at the later stages of the polymerization until aviscous melt is obtained. For many monomers, especially aliphatic oralicyclic monomers, a temperature in the range of 100° C. to 280° C. isadequate.

The reaction time is not critical and is that required to complete thedesired polymerization, e.g., ranges from less than 30 minutes toseveral hours. If desired, with some monomers, room temperaturepolycondensation can be employed and a vacuum is not required.

A polymerization catalyst is not necessary but can be used to shortenreaction time if desired. Conventional catalysts useful for thecondensation of carboxylic acids or esters with alcohols or esterifiedderivatives thereof can be used such as, for example,tetra-n-butyltitanate, tetraisopropyltitanate or hydrated monobutyltinoxide. Such catalysts are effective in the polymerization at aconcentration of at least about 0.01 wt%, preferably about 0.1-0.2 wt%.

The polymerization is preferably conducted under an inert atmospheresuch as nitrogen, helium, or argon.

The hyperbranched polyesters are normally recovered from the reaction assolids or viscous liquids. The polyesters can be purified byconventional techniques such as recrystallization or extraction.

In preparing soluble hyperbranched polyesters of the invention (HBP-1)from aromatic monomers of Formulae I or II, it is preferred that thereactive terminal carboxyl or hydroxyl functions (X or Y), like orunlike, are not attached to immediately adjacent carbon atoms as stericcrowding may inhibit polymerization and branching.

The hyperbranched polyesters HBP-1 contain one X function and numerous Yfunctions in each polymer molecule; many of which are available for postpolymerization reaction with suitable reagents, including capping,linear linking and cross-linking. By "capping" is meant contacting andreacting HBP-1 with a compound (capping agent) containing a functionalgroup which combines chemically with an X or Y function in thehyperbranched polyester; the capped polyester HBP-2 is provided byreaction of some or all of the available HBP-1 functions with cappingagent. The capping agent may also contain other substituents which areinert under capping process conditions. Capping agents include polymersand non-polymeric substances. The purpose of capping is normally to: (i)deactivate the X and Y functions; (ii) attach selected molecules to theHBP-1 molecules, for example polymeric "arms", forming star-shapedstructures; and/or (iii) replace the X and Y functions with othersubstituents having increased activity for desired post-polymerizationreactions.

Suitable capping agents for HBP-1 wherein the residual Y functions arehydroxyl groups (or reactive derivatives thereof) include, for example,anhydrides (acetic, succinic, maleic), acyl chlorides (acetyl,cinamoyl), isocyanates (allyl, 4-bromophenyl, benzyl, cyclohexyl), andbenzylisothiocyanate.

Suitable capping agents for HBP-1 wherein the residual Y functions arecarboxyl groups (or reactive derivatives thereof) groups include, forexample, bases (alkali metal hydroxides and carbonates), alcohols,isocyanates and acyl chlorides. Capping with bases results in HBP-2salts having increased solubility in ionizing solvents. Other suitablecapping agents will occur to those skilled in the art.

Molecules of hyperbranched polyester HBP-1 may be linearly linkedtogether or cross-linked to form HBP-3 products by reacting the residualX and Y functions in HBP-1 with difunctional reagents such as, forexample, diisocyanates (2,4-toluene diisocyanate,1,6-diisocyanatohexane), diols or diacyl chlorides.

Higher order polymeric structures which can be prepared by the postpolymerization processes of capping, linking or crosslinking as justdescribed include, for example: (a) simple end capped hyperbranchedpolymers (HBP-2) which embrace star polymers (represented schematicallyby Formula A below) wherein the arms are provided by a capping agentthat is monofunctional linear polymer; (b) linearly linked polymers(schematic B below) wherein the hyperbranched polymer molecules act asfunctionalized "beads" in a chain; and (c) "nodular networks" (schematicC. below) wherein the hyperbranched polymer behaves as a highlyfunctionalized "nodular" junction point for many linear chains. ##STR1##

Examples of the above structures have been prepared (Examples 10-13)using a hyperbranched polymer prepared from2,2-bis(hydroxymethyl)propionic acid. When the hyperbranched polymerproduct is reacted with 1-2 molar equivalents of a diisocyanate such as1,6-diisocyanatohexane, the polymer loses solubility in THF but retainsit in hexafluoro-isopropanol (HFIP). The inherent viscosity of thereaction product in HFIP increases from 0.15 to 0.32 and the glasstransition temperature (Tg) increases from 42° C. to 53° C. It isbelieved from stoichiometric and steric considerations and productsolubility that this material is a "beaded" polymer chain wherein HBPunits are linearly linked together. As additional diisocyanate is added,loosely crosslinked structures are prepared which become highly swollenin many solvents but remain insoluble. After approximately 5 equivalentsof diisocyanate have been added to the original hyperbranched polymer, atightly crosslinked structure develops, believed to be a "nodularnetwork", which is only slightly swollen by solvents, exhibits a greatlyelevated Tg of 127° C., and is unusually resistant to strong base suchas sodium hydroxide, decomposition taking hours as compared to <5minutes for the original hyperbranched polyester.

Density determinations on the above described products indicate that asthe structure becomes more highly crosslinked the hyperbranched polymernodular network becomes less dense. The overall structure is more openthan the original hyperbranched polyester. The resulting voids betweennodules should be "lined" with functional groups from the nodules andshould be effective in trapping small molecules by means of size and/orchemical reactivity. The highly crosslinked structures of the inventionare chemically and mechanically stable and can be used as catalysts,catalyst supports, column packing material for chromatography, orfilters.

The polyesters (HBP-1) of the invention are known to be very highlybranched for the following reasons:

(i) end group analysis indicates the presence of one X function and alarge number of Y functions in each molecule and a number averagemolecular weight of at least 1500; ¹³ CNMR measurements on aliphatic HBPhave shown 1 branch per 2-3 monomer units;

(ii) clarity of the polymer and the absence of a crystalline meltingpoint, indicating the absence of crystallinity characteristic of linearpolyesters;

(iii) high solubility; and

(iv) a low inherent viscosity typical of highly branched polymers.

The hyperbranched polyesters HBP-1 may be copolymerized with diols ordicarboxylic acids which are polymerizable by melt polycondensation. Theselection of comonomer depends upon the identity of the Y terminalfunctions. Thus, if Y is --OR.increment. the comonomer should be adicarboxylic acid; if Y is --CO₂ R', the comonomer should be a diol.

It will be apparent to those skilled in the art that the hyperbranchedpolyesters of the invention can be "tailored" by controlled linking,crosslinking, copolymerization, and/or partial or complete capping tomodify functionality, thus optimizing their utility in uses such ascatalysts, chromatography packing, or filtering agents.

The comparatively dense, globular, highly functionalized hyperbranchedpolyesters of the invention are also useful as adhesives, drug deliveryagents, rheology control agents in solutions and dispersions for paintsand coatings, and as polymeric binders for paints and coatings. Utilityof these polymers can be further enhanced by changing end groupfunctionality by means of end capping or by crosslinking the globularstructures to produce a highly functionalized "nodular network".

The following experiments illustrate the preparation of monomers ofFormula I wherein R² is R³ N.

EXPERIMENT 1 Preparation of HO(CH₂)₂ N(CH₂ CH₂ COOCH₃)₂

Into 50 ml of methanol was added 6.1 g (0.10 mol) of ethanol amine and20 ml (0.22 mol) of methylacrylate. The resulting mixture was thenstirred unheated for 30 min during which time the temperature rose to35° C. The mixture was then boiled for 4 h, volatiles were removed underhigh vacuum at room temperature and 21.5 g (92%) of alcohol diester as acolorless oil was obtained. ¹ H NMR (CDCl₃): 2.7 (m, 10, CH₂ 's ofacrylate arms and next to N), 3.1 (s, 1, OH), 3.6 (t, 2, CH₂ next toOH), 3.7 (s, 6, CH₃ 's).

IR (neat): 3450 cm¹ (br, w, OH), 1740 cm¹ (s, C=O).

Elemental Analysis for C₁₀ H₁₉ NO₅ :

    ______________________________________                                        Calculated: C, 51.50;  H, 8.15;   N, 6.01                                     Found:      C, 51.80;  H, 8.30;   N, 6.20.                                    ______________________________________                                    

EXPERIMENT 2 Preparation of HO(CH₂)₃ N(CH₂ CH₂ COOCH₃)₂

The procedure of Experiment 1 was repeated using 7.5 g (0.10 mol) of3-amino-1-propanol and yielded 22.5 g (91%) of alcohol diester as acolorless oil.

¹ H NMR (CDCl₃): 1.7 (p, 2, HOCH₂ CH₂ CH₂ (H₂ N), 2.7 (m, 10, CH₂ 's ofacrylate arms and next to N), 3.7 (s and m, 9, OH, CH₂ next to OH andCH₃ 's).

IR (neat): 3450 cm⁻¹ (br, w, OH), 1735 cm⁻¹ (s, C=O).

Elemental Analysis for C₁₁ H₂₁ NO₅ :

    ______________________________________                                        Calculated: C, 53.44;  H, 8.50;   N, 5.67                                     Found:      C, 53.35;  H, 8.51;   N, 5.85.                                    ______________________________________                                    

EXPERIMENT 3 Preparation of HO(CH₂)₅ N(CH₂ CH₂ COOCH₃)₂

The procedure of Experiment 1 was repeated using 10.3 g (0.10 mol) of1-amino-5-pentanol and yielded 24.6 g (89%) of alcohol diester 3 as ayellow oil.

¹ H NMR (CDCl₃): 1.4 (m, 6, HOCH₂ CH₂ CH₂ CH₂ CH₂ (H₂ N), 2.5 (m, 10,CH₂ 's of acrylate arms and next to N), 3.2 (s, 1, OH), 3.6 (t, 2, CH₂next to OH), 3.7 (s, 6, CH₃ 's).

IR (neat): 3450 cm⁻¹ (br, w, OH), 1740 cm⁻¹ (s, C=O).

Elemental Analysis for C₁₃ H₂₅ NO₅ :

    ______________________________________                                        Calculated: C, 56.73;  H, 9.09;   N, 5.09                                     Found:      C, 56.99;  H, 9.07;   N, 4.83.                                    ______________________________________                                    

EXPERIMENT 4 Preparation of p-HOC₆ H₄ CH₂ CH₂ N(CH₂ CH₂ COOCH₃)₂

The procedure of Experiment 1 was repeated using 13.7 g (0.10 mol) fotyramine and yielded 29.6 g (96%) of alcohol diester as a dark brownoil.

¹ H NMR (CDCl₃): 2.6 (m, 12, all CH₂ 's), 3.7 (s, 6, CH₃ 's), 6.4 (s, 1,OH), 6.9 (dd, 4 ArH, J=8.8 Hz).

IR (neat): 3420 cm⁻¹ (br, w, OH), 1735 cm⁻¹ (s, C=O).

Elemental Analysis for C₁₆ H₂₃ NO₅ :

    ______________________________________                                        Calculated: C, 62.14;  H, 7.44;   N, 4.53                                     Found:      C, 62.39;  H, 7.69;   N, 4.55.                                    ______________________________________                                    

EXPERIMENT 5 Preparation of (HOCH₂ CH₂)₂ NCH₂ CH₂ COOCH₃

The procedure of Experiment 1 was repeated except 70 ml of methanol and10 ml (0.1 mol) of methylacrylate were used with 10.5 g (0.10 mol) ofdiethanol amine to yield 17.2 g (90%) of ester diol as a colorless oil.¹ H NMR (CDCl₃): 2.6 (m, 8, CH₂ 's of acrylate arm and next to N), 3.6(m, 4, CH₂ 's next to OH's), 3.7 (s, 3, CH₃), 3.9 (s, 2, OH's).

IR (neat): 3400 cm⁻¹ (br, m, OH), 1735 cm⁻¹ (s, C=O).

Elemental Analysis for C₈ H₁₇ NO₄ :

    ______________________________________                                        Calculated: C, 50.26;  H, 8.90;   N, 7.33                                     Found:      C, 50.02;  H, 8.95;   N, 7.61.                                    ______________________________________                                    

In the following embodiments of the invention, parts and percentages areby weight and temperatures are in degrees Celsius unless otherwisespecified.

Terminal functions X and Y were determined as follows:

Hydroxyl end groups: A 1 g sample of HBP is dissolved in 20 ml of drynitrobenzene, stirred at about 170° C. until dissolved, then reactedwith 2 ml of 3,5-dinitrobenzoylchloride at 115° C. for 10 min. Thereaction mixture is removed from the heat source, stirred 1 min, treatedwith 1 ml of a 1:1 mixture of pyridine and water, heated a furtherminute at 115° C., then cooled to room temperature. The solution istreated with 25 ml of o-cresol and 25 ml of chloroform, then titratedwith 0.1 N ethanolic potassium hydroxide. A blank is run by the aboveprocedure, omitting only the HBP sample. ##EQU1## where A=ml of KOHrequired x N of KOH;

B=ml of KOH required for blank x N of KOH;

C=COOH end groups × g sample used for OH ends/1000.

Carboxyl end groups: A 1 g sample of HBP is dissolved, with stirring, in50 ml of distilled o-cresol at 150° C. The solution is removed from theheat source, stirred a further minute, treated with 4 drops ofbromophenol blue Na salt in 1% ethanol and titrated with 0.04 N KOH inbenzyl alcohol. ##EQU2## where A=ml of KOH required x N of KOH;

B=ml of KOH required for blank x N of KOH.

Inherent viscosity is in dl/g, measured in accordance with W. R.Sorenson and Y. W. Campbell, "preparative Methods of Polymer Chemistry",Interscience, 2nd Ed. (1968), p. 44, on a solution of 0.5 g of HBP in100 ml of m-cresol at 30° C., unless otherwise indicated.

Thermal transitions such as melting point and glass transition point(Tg) were measured with a Du Pont Model 9900 Differential ScanningCalorimeter (DSC) in accordance with B. Wunderlich, "Thermal Analysis",published by Rensselaer Polytechnic Institute (1981).

Density was measured by the Gradient Tube method ASTM D 15056-68.

Degree of branching was determined by carbon nuclear magnetic resonance(CNMR).

HBP products were considered "soluble" in a given solvent if an at least3 to 5 wt% solution of the polymer could be prepared.

EXAMPLE 1 Polymerization of H₃ COOCCH₂ CH₂ N(CH₂ CH₂ OH)₂

Into a 250 ml round bottom 3-necked flask equipped with a mechanicalstirrer, N₂ inlet, reflux-distillation condensor and Wood's metal bathwas added 7 g (0.037 mol) of the monomer prepared in Experiment 5 and2-3 drops of Fascat™ 4102 tin based polymerization catalyst. The mixturewas heated using the indicated cycle until noticeable melt viscosity wasattained. The results are given below.

    ______________________________________                                        Temp (°C.)                                                                        Time (h) Yield     Tg     ηinh                                 ______________________________________                                        100        3                                                                  100        2*                                                                 125        1*       83%       -36° C.                                                                       0.11                                     ______________________________________                                         *Vacuum applied (<0.5 mm)                                                

EXAMPLES 2-5 Polymerization of HOR³ N(CH₂ CH₂ CO₂ CH₃)₂ GeneralProcedure

Into a 250 ml round bottom 3-necked flask equipped with a mechanicalstirrer, N₂ inlet, reflux-distillation condensor and Wood's metal bathwas added one of the monomers prepared in Experiments 1-4 and 2-3 dropsof Fascat™ 4102. The mixture was heated using the indicated cycle untilnoticeable melt viscosity was attained. The results are given in Table1.

                  TABLE 1                                                         ______________________________________                                                                     Time                                             Ex.  R.sup.3    Wt     Temp. (h)  Yield Tg   ηinh                         ______________________________________                                        2    (CH.sub.2).sub.5                                                                         8.0 g  125   2                                                                       150   1                                                                       175   0.5                                                                     175   0.5* 67%   -48  --                               3    C.sub.6 H.sub.4 (CH.sub.2).sub.2                                                         9.0 g  100   1                                                                       150   2                                                                       150   2*   50%    58  0.09                             4    (CH.sub.2).sub.3                                                                         7.0 g  100   0.75                                                                    125   0.50                                                                    150   1.5                                                                     150   1.5* 83%   -39  0.13                             5    (CH.sub.2).sub.2                                                                         7.0 g  100   2                                                                       100   2*   85%   -45  0.08                             ______________________________________                                         *Vacuum applied (<0.5 mm).                                               

EXAMPLE 6 Hyperbranched Polymer form 3,5-Diacetoxybenzoic Acid

Into a 250 ml three-necked round bottom flask equipped with a mechanicalstirrer, Wood's metal bath, N₂ inlet, and distillation column withvacuum attachment was added 6.00 g (0.025 mol) of 3,5-diacetoxybenzoicacid. The solid reaction ingredient was stirred while the polymerizationapparatus was evacuated and purged three times with N₂. The stirred, N₂blanketed mixture was then heated to 200° C. with the Wood's metal bathfor 17 minutes; the bath temperature was then raised to 271° C. over aperiod of 37 minutes. Stirring was stopped and the temperature wasraised to 325° C. over a period of 14 minutes. A vacuum (0.6 mm) wasthen applied to the system for 6 minutes when a very viscous melt wasobtained. The resulting polymer was allowed to cool under nitrogen. Theflask was then broken to recover 3.59 g (81%) of hyperbranched polymerhaving the following properties:

    ______________________________________                                        Tg = 161° C.                                                           Inherent Viscosity = 0.83 (HFIP), 0.17 (THF)                                  Density = 1.3750 g/cc                                                         Solubility: tetrahydrofuran (THF),                                                        hexafluoroisopropanol (HFIP),                                                 dimethylsulfoxide (DMSO),                                                     dimethylacetamide (DMAC), CHCl.sub.3                              Decomposition Temperature = 450° C. (TGA)                              Ends: 6 COOH ends/10.sup.6 g polymer.                                         ______________________________________                                    

The amber polymer was further purified by dissolution in THF followed byaddition of a 20:1 excess of water to precipitate the polymer as a whiteflocculent material.

EXAMPLE 7 Hyperbranched Polymer from 5-Acetoxyisophthalic Acid

Into an apparatus as described in Example 6 was added 6.00 g (0.027 mol)of 5-acetoxyisophthalic acid. The solid reaction ingredient was stirredwhile the polymerization apparatus was evacuated and purged with N₂three times. The stirred, N₂, blanketed material was then heated to 297°C. for 4 minutes. A vacuum (0.2 mm) was then applied to the system fortwo minutes until a very viscous melt was obtained. The resultingpolymer was allowed to cool under nitrogen. The flask was then broken torecover 3.32 g (75%) of hyperbranched polymer which had the followingproperties:

Tg=269.2° C.

Solubility: H₂ O (buffered above pH 7), MeOH, DMSO Inherent Viscosity:0.05 (methanol), 0.08 (DMSO).

EXAMPLE 8 Hyperbranched Polymer from 4-Bromo-3,5-diacetoxybenzoic Acid

Into an apparatus as described in Example 6 was added 10.0 g (0.0315mol) of 4-bromo-3,5-diacetoxybenzoic acid. The solid reaction ingredientwas stirred while the polymerization apparatus was evacuated and purgedwith N₂ three times. The stirred, N₂ blanketed material was then heatedto 277° C. for 20 minutes. A vacuum (0.2 mm Hg) was then applied to thesystem for 2 minutes when a very viscous melt was obtained. Theresulting polymer was allowed to cool under nitrogen. The flask was thenbroken to recover 6.56 g (81%) of hyperbranched polymer having thefollowing properties:

    ______________________________________                                        Tg = 147° C.                                                           Inherent Viscosity: 0.09 (HFIP), 0.05 (THF)                                   Density = 1.6898 g/cc                                                         Solubility:  THF, HFIP, DMSO, DMAC,                                                        o-dichlorobenzene (ODCB), Acetone,                                            CHCl.sub.3                                                       Ends: 229 COOH ends/10.sup.6 g polymer.                                       ______________________________________                                    

EXAMPLE 9 Hyperbranched Polymer from 4,4-Bis(4-acetoxyphenyl)valericAcid

Into an apparatus as described in Example 6 was added 10.0 g (0.027 mol)of 4,4-bis(4-acetoxyphenyl)-valeric acid and 0.3 g of Sb203. The solidreaction ingredients were stirred while the polymerization apparatus wasevacuated and purged three times with N₂. The stirred, N₂ blanketedmaterial was then heated to 227° C. for 3 hours. A vacuum (0.25 mm Hg)was then applied to the system for 10 minutes when a viscous melt wasobtained. The resulting polymer was allowed to cool under nitrogen. Theflask was then broken to recover 8.23 g (98%) of hyperbranched polymerhaving the following properties:

Tg=107° C.

Inherent Viscosity: 0.08 (HFIP), 0.04 (THF)

Density=1.2361 g/cc

Solubility: HFIP, ODCB, Acetone, CHCl₃

Ends: 141 COOH ends/10⁶ g polymer.

EXAMPLES 10-13 A. Polymerization of CH₃ C(CH₂ OH)₂ COOH

Into a three-necked round bottom flask (500 ml) equipped with amechanical stirrer, Wood's metal bath, N₂ and distillation column withvacuum attachment was added 100 g (0.74 mol) of2,2-bis(hydroxymethyl)-propionic acid and about 0.1-0.2 wt% of "Tyzor"TPT organic titanate as catalyst. The solid reaction ingredients werestirred while the polymerization apparatus was evacuated and purgedthree times with N₂. The stirred, N₂ blanketed mixture was then heatedto 200° C. with the Wood's metal bath for 3.5 hours. A vacuum was thenapplied to the system (0.2-0.5 mm Hg) at 200° C. until a viscous meltwas obtained (3.5 hours). The resulting polymer was allowed to coolunder nitrogen. The flask was then broken to recover 72.4 g (84%) ofhyperbranched polyester having the following properties:

    ______________________________________                                        Tg = 42° C.                                                            Inherent Viscosity =                                                                         0.10 (HFIP), 0.05 (THF),                                                      0.06 (methanol)                                                Solubility:                                                                              (3-5% solution, RT); THF, methanol,                                           DMF, N-methylpyrrolidine (NMP), DMAC,                                         Pyridine, Dioxane, HFIP, DMSO, Acetone                             Ends: 273 COOH ends/10.sup.6 g polymer                                        Branching: 1 Branch point/2 linear units                                                 (determined by .sup.13 C NMR).                                     ______________________________________                                    

B. Preparation of Crosslinked HBP-1

Into a 100 ml 3-necked round bottom flask equipped with a refluxcondensor, magnetic stirrer, and heating mantle was added thehyperbranched polyester prepared in Part A and 40 ml of THF. The mixturewas stirred until all of the polymer dissolved. The solution was dividedinto 4 parts. To each part was added 1-3 drops of triethylamine and aquantity of a diisocyanate. The mixture was then refluxed overnight.Results were as follows (all yields were over 95%):

    __________________________________________________________________________        HBP (mol)                                                                           Diisocyanate                                                                             Tg                                                       Ex. g (mol)                                                                             g (mol) ηinh                                                                         °C.                                                                        Comment                                                                             Density.sup.3                                  __________________________________________________________________________    10  5 (0.002)                                                                           0.98.sup.a (0.0054)                                                                   -- --  soluble                                                                             1.2760                                         11  5 (0.002)                                                                           1.40.sup.b (0.0079)                                                                   -- 110 v. swollen;                                                                         1.2492                                                                  opalescent                                                                    gel                                                  12  5 (0.002)                                                                           1.82.sup.b (0.0104)                                                                   -- 125 insoluble                                                                           1.2463                                                                  polymer                                              13  2 (.0008)                                                                           0.34.sup.c (0.002)                                                                    0.32.sup.d                                                                        53 insol THF,                                                                          --                                                                      sol HFIP                                             __________________________________________________________________________     .sup.a 2,4toluene diisocyanate                                                .sup.b 2,4toluene diisocyanate + 1,6diisocyanate hexane                       .sup.c 1,6diisocyanate hexane                                                 .sup.d Inherent viscosity in HFIP                                             .sup.e Bulk density of crosslinked polyester; bulk density of                 uncrosslinked polyester: 1.2962.                                         

The crosslinked polymers prepared using toluene diisocyanate or1,6-hexamethylene diisocyanate, or a mixture thereof, as crosslinkingagents can be ground to 200 to 1000 mesh particles and used as packingmaterial for column chromatography or as filtering aids.

EXAMPLE 14 End Capped Hyperbranched Polymer Capping with AceticAnhydride

Into an apparatus as described for Examples 10-13 was added 1.0 g offinely powdered hyperbranched polyester prepared in Part A of Example10, 50 ml of acetic anhydride, and 1 drop of sulfuric acid. The mixturewas heated to reflux for 1.5 hours. The resulting solution was pouredinto ice water, extracted sequentially with ether, THF and methylenechloride.

The organic layers were then dried with MgSO₄ and evaporated to leave1.46 g of a very viscous liquid polymer. The polymer had Tg of -64.8°C., Mn=11,165 (GPC in HFIP, PET standard, Dispersity=10.1) with 100% ofthe ends of the polymer being acetyl capped (¹ HNMR). THe capped polymerwas soluble in THF, acetone, HFIP, DMSO, and CHCl₃.

EXAMPLE 15 End Capped Hyperbranched Polyester Capping with MaleicAnhydride

Into an apparatus as described in Examples 10-13 was added 0.5 g of thehyperbranched polyester prepared in Part A of Example 10 and 40 ml ofdioxane. The mixture was stirred until all of the polymer dissolved. Tothe solution was added 0.39 g (0.004 mol) of maleic anhydride dissolvedin 20 ml of dioxane. The resulting solution was stirred at least 18hours ar reflux. Removal of all volatiles left 0.43 g of polymerproduct. The polymer had a Tg of 20.0° C. with 30% of the ends of thepolymer being capped (¹ HNMR). The capped polymer was soluble in MeOH,THF, HFIP, and acetone.

EXAMPLE 16 End Capped Hyperbranched Polyester Capping with SuccinicAnhydride

Into an apparatus as described in Examples 10-13 was added 0.5 g of thehyperbranched polyester prepared in Part A of Example 10 and 30 ml ofdioxane. The mixture was stirred until all of the polymer dissolved. Tothe solution was then added 0.40 g (0.004 mol) of succinic anhydridedissolved in 30 ml of THF. Additionally, 0.56 ml (0.004 mol) oftriethylamine and 0.03 g of 4-dimethylaminopyridine were added to themixture. The mixture was then refluxed at least 18 hours. Removal of allvolatiles left 0.67 g of capped polymer product. The polymer had thermaltransitions at -17.9° C. and -6.0° C. and was soluble in THF.

EXAMPLE 17 End Capped Hyperbranched Polyester Capping with Acid Chloride

Into an apparatus as described in Examples 11-14 was added 0.5 g of thehyperbranched polyester prepared in Part A of Example 10 and 40 ml ofTHF. The mixture was stirred until all of the polymer dissolved. To thesolution was then added equimolar (based on acid chloride ends)quantitites of triethylamine and an acid chloride dissolved in 30 ml ofTHF. The mixture was then refluxed at least 18 hours. Quantities andyields of capped polyester obtained with specific acid chlorides areshown below.

    ______________________________________                                                              Yield, g                                                ______________________________________                                        Cinnamoyl Chloride 0.66 g (0.004 mol)                                                                 1.06                                                  Malonyl Dichloride 0.17 g (0.0012 mol)                                                                0.79                                                  N-chlorocarbonylisocyanate 0.42 g                                                                     0.66                                                  (0.0012 mol)                                                                  Terephthaloylchloride 0.24 g (0.0012 mol)                                                             0.38                                                  ______________________________________                                    

EXAMPLE 18 Hyperbranched Copolymer of 2,2-bis(Diacetoxymethyl)-propionicAcid and 3,5-Diacetoxybenzoic Acid

Into an apparatus as described in Example 6 was added 10.0 g (0.046 mol)of 2,2-bis(diacetoxymethyl)-propionic acid and 10.9 g (0.046 mol) of3,5-diacetoxybenzoic acid. The solid reaction ingredients were mixed bystirring while the polymerization apparatus was evacuated and purgedwith N₂ three times. The stirred, N₂ blanketed mixture was heated to227° C. for three hours. A vacuum (0.25 mm Hg) was then applied to thesystem at 227° C. for 2 hours wherein a very viscous polymer melt wasobtained. The polymer was allowed to cool under nitrogen. The flask wasthen broken and 10.4 g (68%) of hyperbranched copolymer was recoveredhaving the following properties:

    ______________________________________                                        Tg = -12.9° C. (small), 33.2° C. (large)                        Solubility:  THF, HFIP, DMSO, DMAC, Acetone,                                               CHCl.sub.3, o-dichlorobenzene                                    Inherent viscosity: 0.10 (THF), 0.23 (HFIP)                                   Density: 1.4605 g/cc.                                                         ______________________________________                                    

EXAMPLE 19 Hyperbranched Copolymer from 2,2-bis(Hydroxymethyl)propionicAcid and 1,1'-Ferrocenedicarboxylic Acid

Into apparatus described in Example 6 added 20.0 g (0.149 mol) of2,2-bis(dihydroxymethyl)-propionic acid and 2.00 g (0.0073 mol) of1,1'-ferrocenedicarboxylic acid. The solid reaction ingredients weremixed by stirring while the polymerization apparatus was evacuated andpurged three times with N₂.The stirred N₂ blanketed mixture was heatedto 200° C. for 2.25 hours. A vacuum (0.6 mm Hg) was then applied to thesystem at 200° C. for 20 minutes when a viscous polymer melt wasobtained. The polymer product was allowed to cool under nitrogen. Theflask was then broken and 16.0 g (84%) of hyperbranched copolymer wasrecovered having the following properties:

Tg=63.7° C.

Solubility: DMSO, DMAC, HFIP

Density: 1.3337 g/cc.

A ¹ H NMR spectrum of the polymer confirmed the presence of the1,1'-ferrocenedicarboxylic acid in the polymer.

EXAMPLE 20 Hyperbranched Copolymer from 2,2-bis(Hydroxymethyl)propionicAcid and Hemin

2,2-Bis(hydroxymethyl)propionic acid (20.0 g, 0.149 mol) and 3.0 g(0.0046 mol) of hemin were allowed to react exactly as described inExample 19. The resulting dark-colored copolymer was soluble in THF,hexafluoroisopropanol, acetone, dimethylacetamide, DMSO and methanol.The polymer showed a Tg at 31° C. and a Tm at 76° C. ¹ H NMR analysisshowed the presence of hemin in the soluble portion of polymer.

EXAMPLE 21 Utility--Dispersions of Hyperbranched Polyester

0.5 g of the hyperbranched polyester prepared in Part A of Example 10was dissolved in 25 ml of ethanol. The solution was divided into five 5ml portions and water was added as follows:

    ______________________________________                                        1      5 ml         clear solution                                            2     12 ml         develops some cloudiness                                  3     18 ml         bluish opalescent disperion                               4     24 ml         bluish opalescent dispersion                              5     234 ml        bluish opalescent disperion.                              ______________________________________                                    

Addition of 1 drop of 1 N potassium hydroxide solution to the dispersioncaused the dispersion to become clear immediately due to decompositionof hyperbranched polyester forming highly water soluble monomer.Addition of 1 drop of concentrated aqueous HCl to the dispersion ofhyperbranched polyester caused some clearing and some polymer to coatthe sides of the container. Addition of 1 drop of Nujol oil to thedispersion of the hyperbranched polyester precipitated the polymer fromthe dispersion.

0.5 g of the hyperbranched polyester prepared in Part A of Example 10was dissolved in 25 ml of THF. The solution was divided into 5 mlportions and various cosolvents were added as follows:

    ______________________________________                                        1       Toluene (1.5 ml)                                                                              polymer precipitated                                  2       CHCl.sub.3 (1.5 ml)                                                                           polymer precipitated                                  3       Hexane (1.0 ml) polymer precipitated                                  4       Water (up to 86 ml)                                                                           bluish opalescent                                                             dispersion.                                           ______________________________________                                    

Dispersions prepared in water (entry 4 in the above table) showed onlyvery slight settling after standing approximately 6 months.Centrifugation was also ineffective in inducing polymer separation fromwater.

Light scattering measurements indicated hydrodynamic radii of 1200Å inboth ethanol and THF. As the samples were further diluted with H₂ O, theradii increased to 3000-4000Å but no precipitation was observed.

EXAMPLE 22 Utility--Drug Delivery

A low molecular weight drug was physically suspended in a "pill"prepared from the hyperbranched polymer prepared in Part A of Example10. The drug diffused out of the pill in less than 24 hours and theintegrity of the pill was maintained. Larger molecules (peptides)suspended in the polymer are released more slowly and uniformly as thepolymer slowly decomposes. The hyperbranched polyester prepared inExample 10, Part A is biocompatable and its degradation products havevery low toxicity. The polymer degrades pH dependently; being mostsensistive to aqueous base. Said polyester degrades within minutes inbase, but remains stable under acidic conditions for hours to days andremains indefinitely stable under neutral conditions.

EXAMPLE 23 Utility--Rheology Modifier

A 300 g sample of the hyperbranched polyester prepared from3,5-diacetoxybenzoic acid as in Example 6 was melt blended at a 5% levelinto a polyarylate. It was observed that the melt viscosity of theoverall blend was reduced.

What is claimed is:
 1. A polyester prepared by reacting the X and Yfunctions of a soluble hyperbranched polyester having at least 1 branchper 10 monomer units prepared by conventional polycondensation of one ormore monomers of the formula:

    XR.sup.2 [(R.sup.1).sub.m Y].sub.n

wherein: R¹ is a divalent C₁₋₁₂ hydrocarbyl radical which is linear orbranched aliphatic, alicyclic, aromatic or mixed aromatic-aliphatic; R²is a C₁₋₁₂ hydrocarbyl radical having a valence of (n+1), which radicalis linear or branched aliphatic, alicyclic, aromatic or mixedaromatic-aliphatic, or R² is r³ N wherein R³ is defined as for R¹ ;either of R¹, R² or R³ optionally also containing substitutents that areunreactive under processing conditions; X and Y are terminal functionsselected from --CO₂ R' and --OR.increment. wherein R' is H or C₁₋₁₂alkyl and R.increment. is H or OC(O)R; M is 0 or 1; and n is an integerand is at least 2: with the provisos that:(i) both X and Y are not --CO₂R' or --OR"; (ii) no X or Y function is adjacent to another X or Yfunction; (iii) when R² is an aliphatic hydrocarbyl radical, Y is --CO₂R'; and (iv) when R² is R³ N, m is 1; with a difunctional reagent. 2.The polyester of claim 1 wherein the X and Y functions have been reactedwith a diisocyanate.
 3. The polyester of claim 2 wherein sufficientdiisocyanate is reacted to create a linearly linked polyester.
 4. Thepolyester of claim 2 wherein sufficient diisocyanate is reacted tocreate a nodular network polyester.
 5. A polyester prepared by reactingthe X and Y functions of a soluble hyperbranched polyester having atleast one branch per 10 monomer units, said polyester being prepared byconventional polycondensation of one or more monomers of the formula:

    XR.sup.2 [(R.sup.1).sub.m Y].sub.n

wherein R¹ is a divalent C₁₋₁₂ hydrocarbyl radical which is linear orbranched aliphatic, alicyclic, aromatic or mixed aromatic-aliphatic; R²is a C₁₋₁₂ hydrocarbyl radical having a valence of (n+1), which radicalis linear or branched aliphatic; either of R¹ or R² optionally alsocontaining substituents that are unreactive under processing conditions;X is CO₂ R'; Y is OR.increment., wherein R' is H or C₁₋₁₂ alkyl and R"is H or OC(O)R'; m is 0 or 1; and n is an integer and is at least 2;with the proviso that:(i) no X or Y function is adjacent to another X orY function with a difunctional reagent.
 6. The polyester X and Y ofclaim 5 wherein the X and Y functions have been reacted with adiisocyanate.
 7. The polyester of claim 6 wherein sufficientdiisocyanate is reacted to create a linearly linked polyester.
 8. Thepolyester of claim 6 wherein sufficient diisocyanate is reacted tocreate a nodular network polyester.